The bulk, living polymerizations of 3/4-(chloromethyl)styrene (CMS) in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) gave rise to rapid reaction. The CMS polymerization (no accelerant) proceeded at a rate similar to living styrene polymerizations accelerated with camphorsulfonic acid under comparable reaction conditions. The living nature of the CMS polymerization was confirmed by NMR evidence for TEMPO termination and by chain extension studies on TEMPO-terminated CMS homopolymer. Block and random copolymer synthesis was also demonstrated for this system. Styrene and CMS can interchangeably be used in the block formation.